Azo dyestuff derivatives of aminobenzo-p-dioxans



Patented July 3, 1945 UNITED sTATss wam OFFICE AZO DYESTUFF DERIVATIVES OF AMINO- BENZQ-p-DIOXANS Robert C. Conn and Frederic H. Adams, Bound U l l, H Brook, and John P. GouldingQNeshanic Station, N. J., assignors to American Cyanamid Coma j pany, New York, N. Y., a corporation of Maine No Drawing.

Application December 10,1943, Serial No. 513,737 l i 9 Claims. (01. 260-152) This invention relates to a .IIBWSBIlBS of azo dyestuffs derived from mohoamino-benzO-paradioxans, the dyestufis being obtained by diazotization and couplingfiof N-substituted derivatives of. such aminobenzodioxans as 6-amino-1,4- benzodioxan having the formula 1 a series of bases suitable for the production of other azo dyesand to develop such dyestherefrom..

In general; the principalobjects of the present invention are accomplished by condensing, the amino-henzo-para-dioxan with a. pararnitrohalogenobenzene and subsequently reducing the nitro group to anamino group. The resulting new compounds, afterdiazotization and coupling,

yield dyestuffs which have desirable properties.

Either para-nitrohalogenobenzene or a para-w nitrohalogenobenzene containing a negativessubor 7-amino-benzo-para,- dioxeno para dioxan having the analogous formula the N-substituent being a para-'amino-phenyl radical. The latter may berepr'esented and numbered for the purposes of the present invention in which X may represent a hydrogen, halogen,

cal-boxy or sulfonic radical, the acyl radical of a carboxylic acid or a sulfonarnide group.

The instant application relatesfto new azo dyestuffs, particularly to ice-colors, Whichpossess novel color shades and unusual light fastness.

The N-para-amino-phenyl substituted aminobenzo-para-dioxans per. se comprise the subject matter of our copendingapplicationfor United States Letters Patent, Serial No. 513,734, filed of even date.

Very few aromatic aminocompounds have been known which produce ondiazotization and coupling with an icecolor coupling component strong blue to violet shades. It is one of the principal objects of the present invention to produce a new series of bases and ice-colors derived therefrom which will have these desirableshades. It

is a, further object of the invention to produce stituent ortho to the halogen radical may be used as a starting material. These negative substituents may include radicals such as halogen, nitro, carboxy, or sulfonic radicals, the acyl radical of acarboxylic acid or sulfonamide or group. In. any case, after condensation and reduction the product constitutes. an N-para-'aminophenyl.-

substituted aminobenzodioxan. "Therefore as used in the instant application, the expression a para-.aminophenyl radical? includes not only the lpara-amino-phenyl radical, but also those.

group, but also N-substituted-sulfonamides. In the latter case, the sulfonamide group may be onein which either o r bothof'the hydrogens are substituted by an alkyl or aryl radical "or one in which the substituents form with the nitrogen a heterocyclicring such as a sulfonpiperidide,

'sulfonmorpholide or the like.

Those para-nitrohalogenobenzenes containing negative substituents, orthoto the halogenradi cal, are particularly useful. When. such'materials are used, condensation proceeds smoothly in aqueous media. The invention, however, is not necessarily so limited. Condensation may be carriedout in any solvent compatible with the solubility and reactivity of the particular nitrohalogenobenzenej employed. In some cases, an

anhydrous solvent suchas nitrobenz ene or the ducing agents.

like .is required. In some cases, also, the use of such as a metal oxide, carbonate or the like.

Reduction of the nitro to an amino group may be carried out either by alkaline or by acidic re- The pH will determine whether free bases or salts will be produced. It will be apparent that two different types of salts are possible. vThere'may be acid salts of the base. On the other hand, when an. acidic substituent such as a carboxylic or sulfonic group is present on the .p-aminophenyl radical, the acidic con stituent may be neutralized to form a salt. Both types of salts as well as the .free bases are useful. Each may be converted to the other by appropriate treatment. Reference to the new bases erable. These produce, when coupled with the diazotized bases of the present invention, the most desirable blue to violet shades.

However, the invention is not necessarily so limited. Among'other ice-color coupling components which produce useful products may be listed by way of example such compounds as beta-naphthol, amino-z naphthol, benzoyl napthols; pyrazolones 8 -amino-2-naphthol, 8-acetyland pyrazyl pyrazolones hydroxy benzofluorenones; hydroxy derivatives of phenyl naphthylamines such as 7-hydroxy-1-naphthyl-m hy- A droxyphenylamine; particularly the various N- substituted amides such asarylides of 5,6,7,8-tetrahydro-2- hydroxy3-naphthoic acid, of 2-hydroXy-3-anthroic acid, of methyl and dimethyl salicyclic acids, of hydroxy carbazole carboxylic in the instant specification and claims is there-Q. fore intended to include not only the bases them-.

selves but also both types of salts thereof.

Diazotizati'on of some bases of the presentinvention in mineral acid solution by nitrous acid produces, according to the conditions imposed, two diiferent products. In general, use of higher temperatures; greater concentration of the base in solution, higher mineral acid concentration and excess nitrous acid generally lead to formation of an N-nitroso derivative of the diazonium salts. Lower temperature, lower acid concentrations and controlled nitrous acid addition lead toformation of the diazonium chloride itself.

acids, of hydroxy benzocarbazole carboxylic acids,

10f. hydroxy-benzoacridone carboxylic' acids, of

In general, the N-nitroso diazotization prod- I I ucts lead to the production of different, duller and less desirable shades when coupled. The simple 'diazotized product leads to the production of the more valuable and faster shades.

Con-

version of the N-nitroso colors to the more deysis of the former. This may be accomplished by heatingthe N-nitroso derivatives in dilute solutions'of some alkaline material such as soda ash or the like. Reducing agents such as so diumsulfide, sodium bisulfite or their equivalents may be included in the saponification bath to destroy nitric oxides as they are liberated.

Intheir diazotized'form, the bases may be coupled either with orwithout a substrate, to yield dyestuffs or'pigments of great value because of their strength, variety of shade and fastness properties. In particular, however, the bases of the present invention are important for the production of fast blue prints or dyeings 'upon cellulosic materials. These are produced in general, by impregnating the cellulosic material in alkaline baths with appropriate ice-color coupling components and then printing solutions of the diazotized bases which have been buifered and thickened upon such prepared cloth, or by pad of the diazotized'bases or of the diazo salts.

,sirable shades is accomplished through hydrol- 3,7 dihydroxy-naphthalene-2,6-dicarboxylic acid,

of hydroxy-dibenzofuran carboxylic acids, ofhydroxy benzothi'ophene carboxylic acids, etc., and the arylides of acetoacetic acid, furoyl acetic acid, benzoylacetic acid, terphthaloyl-bis-acetic acid and the like.

tive or of a naphthylarnine, or it may be the radical of a heterocyclic amine, such as, e. g., of an amine of the benzothiazole series or of a diamine I of the diphenylene oxide or diphenylene sulfone a stuffs suitable for dyeing vegetable or animal, fibers. In this case, agreat many of the customary phenolic or aminic coupling components may be used. The coupling component, however,

must carry at leastonesulfonic group incase the diazo component has none. Illustrative examples of such coupling components include salicyclic acid, resorcinol, .m-phenylene diamine,

the large number of naphthol-sulfonic acids such as e. g., R acid, G acid, the Cleves acids, J acid, Gamma acid, J-acid urea and J-acid imide, H acid and many others.

. ionic derivatives of 1-phenyl-3-methyl pyrazo- The bases of the present invention may be also converted into diazo-sulfonates. If the basic portion of these diazo-sulfonates is free from solubilizing groups, they may be blended with appropriate ice-color coupling components andoxidiz'ingagents. Such blends may be incorporated into a printing paste, printed on vegetable fibers and the pigment developedby treatment with steam. l A

Substantially any of the ice-color coupling components are generally useful for production of insoluble, developed dyes, and-enablethe production of a variety'of colors from yellow to blue.

However, for the present purposes, the use of arylides of Z-hydroxy-B-naphthoic acid is preflone-5also may be used. l

If so desired, the new diazo components of the present invention also may be used for the production of disand'poly-azo dyes in accordance with the customary procedures. Depending upon their structure, the dyes obtained from the new bases are direct dyes, acid wool dyes or chrome dyes. In each group, a great many of them have very valuable dyeing and fastness properties.

The invention will be more fully illustrated in conjunction with the following examples which are meant to be illustrative only and not by way of limitation. All parts are by weight unless otherwise noted.

' Example 1 133 .parts of sodium '2-chloro- -5-nitrobenzene sulfonate (61.8% purity) are condensed with 55.8

parts of 6-amino-1,4-'benzodioxan in 400 parts of water in; the presenceof 50 parts of calcium carbonate by refluxing the mixture until reaction is substantially complete. Then 600 parts of water and 12 parts of ammonium chloride-are introduced, and at reflux temperature 80. parts of zinc dust are added in successive small portions. When the reaction mixture has become colorless, it is clarified and parts of hydro- 'chloric acid (1.19) are added. The precipitated I The arylide group in the couplingcomponent may be a'simple' aromatic group such .as the radical of aniline or of an aniline deriva- Pyrazolones such as sulmagnesium sulfate di-hydrate. color mixture are dissolved in 25.5 parts of water containing 2 parts of sodium acetate and0.5 f

product is separated by filtration and washing with water 01! the filter. It has the formula HrN I sole h it ExampZeZ i 20, part of N (2'-sulfo-4+amino .phenylifiamino-Li-beiizodioxan obtained in" Example 1 are heated at reflux for 7 hours in 300 parts of hydrochloric acid containing 3 parts of stannouschloride, Completion of the reaction is indicated by'the fact that,no,alkali-soluble mate- 0.8 part of the amine of Example 2 is dissolved in 4 parts of alcoliol'and run at 0., into a solution of 9 parts of zinc chloride and 0.3 part of sodium nitrite in 10lparts of water. The precipitated product is filtered and the residue iswashed with 20" parts i of water. l The washings, are com binedwith the first filtrate and sodium chloride is added to complete precipitation. The precipi- SOaNa tated zinc chloride double salt is filtered and dried under vacuum. l U I Example 4 The zinc chloride double salt obtained in Ex ample 3 is mixed with one-third of its weight of 2 pa'rtsof this part of. acetic acid. '70 parts of a suitable carbohydrate thickener are added. This color pasteis printed from an engraved roll on cotton piece goods previously impregnated with the ortho-toluidide of 2-hydroxy-3-naphthoic acid from an alkaline solution, and the printed stripe is passed through a dilute soda ash solution at 35 0., then soaped at the boil and finished by passing through a boiling 5% soda ash solution. A bright blue dyeing results with very good fastness properties.

Example 5 When the alpha-naphthylamide of 2 -hydroxy- 3-naphthoic acid is substituted for the orthotoluidide and the procedure of Example}; is repeated, a blue of greener shade is obtained.

Example 6 i 1.15 parts of the zinc chloride double saltproduced as in Example 3 are dissolved 11140 parts of water and 0.32 partof anhydrous sodium sulfite, dissolved in 2 /2 parts of water added, i01- lowed by 0.26 part of sodium carbonate. The reaction mixture is clarified by filtrationand 14 parts of sodium chloride added tothe filtrate. The precipitated sodium diazo sulfonate is filtered and dried. 3.5'7parts of the sodium diazo sulfonate are well mixed with 263 parts of 2-hydroxy-3 naphthoic acid anilide. This color mixtureis dissolved in water together with sodium *chromate and the solution is treated with a suitable thickener. The resultant paste is'printed on cotton piece goods from an engraved roll, the printed stripe then being dried and steamed. After soapblue shade.

ing and drying the patternis"printedagreenish- Example 7 I 1.6 parts of N-(T-sulfo l amino phenyD- G- amino-1,4-benzo-dioxene as obtained in Example 1 are stirred in 25 parts of water and are dissolved by adding 0.2 part sodium hydroxide 'llo .the clear solution areadded 2:5 parts oi hydro -r color results, coupling being complete in about 15 minutes. At 70 C., the dyestuif is salted out, by adding 20.0 parts of sodium chloride. After stirring for 15 minutes, the precipitate is filtered oiI,

washedon the filter with 10% saltsolutionland dried at 45 C. The resultant product isa deep blue-black powder readily soluble in waterlyieldg ing a bright blue solution, and has the following formula: y r

Example 0.5 part of the dyestuff as prepared in Example '7 is'dissolved in 500 parts of water. One-tenth of this solution is diluted with parts or water and 4.0 parts of sodium chloride dissolved in the solution. 5.0 parts of previously wet-out cotton piece goods are entered intothe dye bath. While agitating the cloth, the temperature of the: dye

bath is raised to and maintained at the boil for one-half hour. At this time, the cloth is removed,

rinsed in .fresh water, treated at 65? C. in a 1%- soapsolution, rinsed again and dried. .The cotton piece goods is levelly dyed a bright blue of reddish shade.

. simple 9 One-tenth partof the standard dye solution as prepared in Example. 8 is .diluted with 150 parts of water, and then 2.0 parts of sodium sulfateand 2.0 parts of 5% sulfuric acid solutionare added; 5.0 parts of well boiled-out wool flannel are, en tered in this dye bath and whilefagitating-efii ciently the temperature is raised to the boil. After boiling for three-quarters of an hour, the cloth is removed, rinsed with freshwater, heated at 65? C. in a 1% soap solution, rinsed in fresh water i and dried. The wool flannel is dyed levelly a brilliant corinth.

-,Emamrle 10 I A dia'zoslurry is prepared as described in Example 7. This is stirred into a cold solution of 0.98 part of acetoacetanilide in 50 parts of water containing 0.23part of sodium hydroxide and 2.6 parts of soda ash. A tan precipitateforms immediately. When coupling is complete, the temperature is raised to 40 C. and 15.0 parts of sodium chloride added. The brown precipitate is filtered offand is dried at 45 C. A brown powder results which dissolves readily in water, yielding a yellow solution, and has the following formula: V

0.2 part or the dyestufi preparedin Example'lo is dissolved in200 parts of water .towhichis'added 2.0p'arts of sodium sulfate and 2.0 parts of 5% sulfuric acid. 5.0 parts of wool flannel previously well boiled 'out'are entered and the solutionis gently boiled for'one-halfhour; The cloth is'removed, rinsed in fresh water, heated at 65 C. in 1% soap solution, rinsed in fresh water and dried. A strong,- golden yellow dyeing' results.

Example 12 38.8 parts of benz o-para-dioxeno para-dioxan are dissolved in 420 parts of glacial acetic acid containing 30 parts of sulfuric acid (1.84) and are nitrate d at 30 C. by the addition of 12.6 parts ofa mixed acid (28% nitric,acid;-56% sulfuric acid). The temperature is maintained at 30 -50 during the addition of the mixed acid and thenis held at 50-60 C. for about 30 minutes. After drowning in icejand water and stirring until solidification is complete, '7-nitro-benzo-para-di oxeno-para-dioxan is separated by filtration. On recrystallization from alcohol, the product melts at 130-13l C. It has the formula Example 13 33 parts of the nitrobenzo-para-dioxeno-paradioxan produced in Example 1 are. dissolved in 800 parts of water containing 6.5 parts of glacial acetic acid, 70 parts of ironfilings added and'the mixture stirred at 60 C. for about seven hours.

260 parts of benzene are added at the boiling point and the reaction mixture is cooled to room temperature. After filtration and separation of the benzene layer, the aqueous layer and residue are again extracted with 180 parts of hot benzene. The benzene extracts are dried. Addition of dry hydrogen chloride separates the hydrochloride whichis filtered off, dissolved in water, the water solution clarified and the free amine precipitated by neutralizing, the solution with soda ash. Crystalized from alcohol, the 7 -amino-benz'o-paradioxeno para-dioxan melts at 95-96' C. It has the formula QHi Example 14 5 parts of 7.-amino.-benzo-para-dioxeno-paradioxan are condensed with 7.7 parts of the sodium salt of 2-chloro-5-nitrobenzene sulfonic acid (89%) in 80 parts of water containing 2 parts of alcohol and 4 parts of calciumcarbonate at the reflux for 48 hours. The reaction mixture is filtered while hot, and l0' parts of ammonium chloride in 150 parts of water are. added to the filtrate. The resultant mixture is brought to the boil and '7 parts of zincdust are strewnin portionwise. When the reaction mixture has become decolorized, it is filtered while hot, the filtrate acidified with acetic acid and the resultant white precipitate separated by filtration. The product, N (2i sulfo -e'-aminophenyl) -"7 -amino-benzopara-dioxeno-para dioxane has the formula Example 15 The N-(2"'-sulfo-4'-amino phenyl)-7-aminobenzo-para-dioxeno-para-dioxan produced in Example 14 is refluxed in 165 parts of 20% hydrochloric acid until solution is complete. The reaction mixture is clarified in the presence of decolorizi'ng charcoal and treated with an excess of caustic. The alkaline solution is'extracted with ether and the ethereal solution dried; Addition of dry hydrogen chloride precipitates the N-(4'- aminophenyl) 7 amino benzo' para-dioxenopara-dioxan hydrochloride. The compound has the following formula:

The hydrochloride of Example 15 is diazotized in dilute hydrochloric acid solution at room temperature by the addition of sodium nitrite to a permanent test against starch iodide paste. The

diazo solution so prepared is buffered to a nega tive acid 'test against Congo Red test paper by addition of sodium acetate solution and then Example 17 -Dyestuffs of distinctive colors valuable because of brightness and general fastness properties are obtained by diazotization of N-(2'-sulfo-4'-aminophenyl). 6 amino-lfl-benzodioxan and-coupling of the resulting diazo compound with a varietyof coupling components. The following list illustrates some of the dyestuffs obtainable and the shades produced intheirapplication; g1

5,5-dihydroxy 2,2 dinaph l-naphthylamlne Dyestufis A Color of dye Acid wool dyeing Direct cotton dyeing N-(2-sulio-4-aminophenyl) Black 6 a min o-l,4-benzodioxan 2 -hydroxynaphthalenc 3,6 disulfonic acid v 6-amino-1,4benzodioxan Z-amino -hydroxynaphthalene- 7-sulfonic acid 6-amino-1,4-benzodioxan 1 (4-sulfophenyl) 3 -methyl pyrazolone-5 Black.

Dark brown Red-brown Maroon.

Black;

6-amino-1,4-benzodioxan thylamine-7,7-disulfonic acid N-(2-sulfo-4-aminophenyl) I i (acid) (i-amino-lA-benzodioxan l-amino 8 hydroxynaphtha 1ene-3,6-disulfonic acid aniline (alkaline) N-(2'-sulfo-4-aminophenyl) i fi-amino-1,4-benzodioxan Z-hydroxy benzoic acid N-(2'-su1io-4-aminopheny1) 1 6-amino-1,4-benzodioxan 1,3-dihydroxy benzene 1- II (alkaline) Sulfanilic acid N-(2-sulfo-4-aminophenyl) 1 (acid) 6-amino-1,4-benzodioxan do Corinth.

Brown);

Dark brown Chocolate.

Black 1. (Diazotized) 1-naphthylamine-7-sulfonic acid J, (Diazotizcd) N-phe11y1-5-hydroxy-2-naphthylamine-7-sulfonic acid Dark brown.

Navy

Khaki (top-chromed).

Brown-black Green-blue.

Blue.

We claim:

1. New azo dyestuffs of the general formula A-N=NB in which A is the residueof a coupling component and B is the residue of an N- para-amino-phenyl-substituted heterocyclic compound selected from the group consisting of 6- aminobenzo-para-dioxan, and 7-amino-benzopara-dioxeno-para-dioxan.

2. New azo dyestuffs according to claim 1 in which A is the residue of an ice-color coupling component. A

3. New azo dyestuffs according to claim 1 in which A is the residue of an aryli-de of 2-hydroxy- 3-naphthoic acid.

4. New azo dyestuffs of the general formula AN=N-B inwln'ch Ais the residue of a coupling component and B is the residue of an N-(4'-amino-2-sulfo-phenyl) substituted heter ocyclic compound selected from the group consisting of fi-aminobenzo-para-dioxan and 7-aminc-benzo-para-dioxeno-para dioxan.

5. An azo dyestuii having the formula in which A is the residue of an ice-color coupling component.

6. An azo dyestuff according to claim 5 in which A is the residue of an arylide of 2-hydroxy- 3-naphthoic acids 7. An azo dyestuff according to claim 5 in which A i the residue of an arylide of the henzene series of 2-hydroxy-3-naphthoic acid,

8. An azo dyestuff according to. claim 5 in which A is the residue of the p-naphthylamide of 2-hydroxy-3-naphthoic acid. l

9. An azo .dyestuff according to claim 5 in which Ais the residue of the orthophenetidide of 2-hydroxy-3-naphthoic acid.

ROBERT C. CONN. FREDERIC H. ADAMS. JOHN P. GOULDING. 

